Quaternary ammonium sulfamates



United States Patent Ofiiice 3,223,794 Patented Dec. 14*, 1%65 3,223,704 QUATERNARY AMMONIUM SULFAMATES Wiiiiam J. Shihe, in, Riverton, N.J., and Marcus Sitter:- iield, Phiiadelphia, Pa., assiguors to Hollichem Corporation, Camden, N.J., a corporation of New Jersey No Drawing. Filed Oct. 27, 1961, Ser. No. 148,029 7 Claims. (Cl. 260-2471) This invention relates to quaternary ammonium compounds, and it specifically relates to the products resulting from the reaction of quaternary ammonium and certain organic sulfamates.

Quaternary ammonium compounds have heretofore been known to possess germicidal and fungicidal properties; however, these desirable properties were at least partly offset by their irritating effect on the skin and other bodily surfaces when such surfaces are exposed thereto. They were, furthermore, generally unpleasant to the taste so that they could not readily be used for oral hygiene purposes and the like.

It has now been discovered that certain organic sulfamates, when reacted with quaternary ammonium compounds, form products which are at least as biocidally active as the ordinary quaternaries and which are, additionally, devoid of undesirable side reactions on the skin and other bodily surfaces as well as on fabrics and the like. Furthermore, certain of such products are sweettasting and, therefore, particularly suitable for oral hygiene purposes.

The quaternary ammonium radical of compounds embodying the present invention may be selected from any of the well-known class of quaternary ammonium compounds; for example, the alkyl quaternaries such as lauryl trimethyl ammonium, stearyl trimethyl ammonium, stearyl dimethyl ethyl ammonium, cetyl dimethyl ethyl ammonium, myristyl dimethyl ethyl ammonium, lauryl dimethyl ethyl ammonium, tallow trimethyl ammonium, hydrogenated tallow trimethyl ammonium, coco trimethyl ammonium, di-hydrogenated tallow dimethyl ammonium, di-coco dimethyl ammonium, di-soya dimethyl ammonium, hydrogenated tallow dimethyl ethyl ammonium, coco dimethyl ethyl ammonium, tallow dimethyl ethyl ammonium and soya dimethyl ethyl ammonium; the alkylaryl quaternaries such as lauryl dimethyl benzyl ammonium, alkyl dimethyl benzyl ammonium, cetyl dimethyl benzyl ammonium, stearyl dimethyl benzyl ammonium, alkyl dimethyl dichlorobenzyl ammonium, alkyl dimethyl ethyl benzyl ammonium, alkyl dimethyl dimethyl benzyl ammonium, dodecyl benzyl trimethyl ammonium, dodecyl methyl benzyl trimethyl ammonium, octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium, soya dimethyl benzyl ammonium, hydrogenated tallow dimethyl benzyl ammonium, tallow dimethyl benzyl ammonium and coco dimethyl benzyl ammonium; the alkyl and alkylaryl pyridiniums such as coco pyridinium, cetyl pyridinium and dodecyl benzyl pyridinium; the alkyl and alkylaryl isoquinoliniums such as alkyl isoquinolinium, cetyl isoquinoliniurn and dodecyl benzyl isoquinolinium; the alkyl and alkylaryl picoliniums such as alkyl alpha picolinium, alkyl beta picolinium and alkyl gamma picolinum; the imidazoliniums such as alkenyl benzyl hydroxyethyl imidazolinium, alkenyl dichlorobenzyl hydroxyethyl imidazolinium, alkenyl ethyl benzyl hydroxyethyl imidazolinium, alkenyl dichlorobenzyl hydroxyethyl irnidazolinium, coco benzyl hydroxyethyl imidazolinium, coco ethyl hydroxyethyl imidazolinium, stearyl ethyl hydroxyethyl imidazolinium, stearyl benzyl hydroxyethyl imidazolinium, stearyl dichlorobenzyl hydroxyethyl imidazolinium and stearyl ethyl benzyl hydroxyethyl imidazolinium; the morpholiniums such as coco methyl morpholinium and myristyl methyl morpholinium; and the N-pyridiniums such as N-(stearoyl colamino formyl methyl)-pyridinium and N-(lauroyl colamino formyl methyl) -pyridinium.

The sulfamate radical may be selected from any organic sulfamate and more specifically, may be either an aliphatic, an aromatic, a cyclic or a heterocyclic derivative of sulfamic acid. An example of an aliphatic derivative is n-hexyl sulfamate, of a cyclic derivative is cyclo hexyl sulfamate, of a heterocyclic derivative is piperidine sulfamate and of an aromatic derivative is aniline sulfamate.

Each of the above-mentioned types of compound can be prepared in a similar manner with variations depending primarily on differing molecular Weights of the components. In general, the method of preparation comprises mixing stoichiometric amounts of the selected sulfamate and the selected quaternary ammonium salt in an aqueous solution, at ambient temperatures and pressures, whereby both reactants are dissolved in the water at approximately 25% strength and react with each other under vigorous agitation. In most instances, the reaction product separates as a liquid; therefore, to facilitate separation, an excessive amount of the reactants is used, the aqueous layer is separated and the non-aqueous layer is Washed and dried under reduced pressure or in a forced draft oven.

The following examples are illustrative of the preparation of compounds embodying the present invention:

Example 1 380 grams (0.5 mol) of alkyl dimethyl benzyl ammonium chloride, at 50% strength, is diluted to 25% strength with deionized Water. grams (0.5 mol) of sodium cyclo hexyl sulfamate is dissolved in 300 grams of deionized water. The quaternary solution is then intermixed with the sulfamate solution accompanied by rapid and vigorous agitation. The resulting oil layer is then separated, washed and dried under reduced pressure. The end product, when dried, is a waxy, light yellow product and has a sweet taste.

Example 2 265 grams (0.5 mol) of a 50% aqueous solution of dodecyl trimethyl ammonium chloride is diluted to 25% strength with deionized water. 100 grams of sodium cyclo hexyl sulfamate is dissolved in 300 grams of water. The two solutions are intermixed and blended. There is no separation since the dodecyl trimethyl ammonium cyclo hexyl sulfamate is completely Water-soluble. The reaction product is isolated by removing the water by evaporation under reduced pressure or in a forced draft oven at F. The residue is then dissolved in 99% isopropanol and filtered to remove any salts. The alcoholic filtrate is then evaporated to remove the alcohol. The end product is a yellow waxy material completely soluble in water and having a sweet taste.

Example 3 350 grams (1 mol) of anhydrous dodecyl benzyl trimethyl ammonium chloride is dissolved in isopropyl alcohol to make a 25% solution. grams (1 mol) of cyclo hexyl sulfamic acid is dissolved in isopropyl alcohol to make a 25% solution. The two alcoholic solutions are then blended together: 56 grams of KOH pellets are then added and the mixture is thoroughly agitated. The resultant salt is removed by filtration to provide a filtrate comprising an alcoholic solution of dodecyl benzyl trimethyl ammonium cyclo hexyl sulfamate. Upon evaporation of the alcohol, there is provided an end product which is low melting and has a waxy appearance. If desired NaOI-I may be substituted for the KOH.

Example 4 The same procedure is carried out as in Example 3 except that the KOI-I or NaOH is first dissolved in iso- 3 propyl alcohol and then a stoichiometric amount of this latter solution is used in place of the pellets.

The above examples are specific to the preparation of cyclo hexyl sulfamates: however, the previously mentioned aniline, n-hexyl and piperidine sulfam-ates, as well as all other equivalent sulfamates, are prepared in the same manner and in the same proportions, mol for mol, whereby only the particular weights differ depending on the molecular weights of the specific compounds involved.

Illustrative of the biocidal properties of the compounds of the present invention are b acteri ostatic tests whereby each of cyclo hexyl, n-hexyl, aniline and piperidine sulfamiates were used against E. typhosi, E. coli and Staphylococcus aureus. All of these compounds exhibited effective inhibition against Staphylococcus aureus in concentrations as low as 1 part in 10,000 in aqueous solution. They also exhibited effective inhibition against E. coli in concentrations of 1 part in 1,000. A ainst E. typhosi, all we hibited effective inhibition at a concentration of 1 part in 1,000 and the aniline sulfam-ate proved effective in concentrations even as low as 1 part in 10,000.

The compounds of the present invention may also be complexed with halogens, such as bromine and iodine, to form addition products having enhanced germicidal properties, these products being free from the toxic, irritating and di-scoloring effects of free halogens. Such halogen complexes are easily prepared by dilulting the selected quaternary ammonium halide salt to 10% and the-n heating to about 160 F., after which the selected halogen or halogen complex or halogen solution is added slowly with rapid agitation. The mixture is then cooled to about 75 F. and a stoiehiometric amount of the sodium salt of the sulfamate in 10% aqueous solution is added. Purification then follows the normal procedure as in the examples above.

The quaternary ammonium sulfamates of the present invention are substantive to both skin and fabrics and are generally water-soluble. They may be used in a variety of liquid and solid compositions where an effective nontoxic, non-irritating, substantive biocidal ingredient is desirable. Furthermore, certain of these compounds, such as the cyclo hexyl sulfamates, are highly desirable because of their sweet, pleasant taste when the composition is utilized for oral hygiene purposes. The following examples are illustrative of such compositions:

Example 5 A biocidally active, sweet-tasting tooth paste is prepared as follows:

Component: Parts by wt. Glycerin 23.0 Gum tragacanth mucilage (5% in H O) 14.0 Precipitated chalk 49.9 Bentonite 3.0 Sodium lauryl sulfate 3.0 Water 7.0 Dodecyl trimethyl ammonium cyclo hexy sulfamate 1.0

All the above ingredients are thoroughly intermixed at ambient temperatures to form a homogeneous paste.

Example 6 A biocid-ally active cold cream is prepared as follows: Component: Parts by wt. Mineral oil 47.9 Beeswax 6.0 Spermaceti 6.0 Cetyl alcohol 1.0 Lanolin 1.0 Water 38.0 Perfume 0.1

Alkyl dimethyl benzyl ammonium aniline sulfamate 0.1

The mineral oil, beeswax, spermaceti, cetyl alcohol and lanolin are mixed with the 'alkyl dimethyl benzyl ammonium aniline :sulfamate and the mixture is heated to form a melt. It is then cooled to 50 C. and water is added with continuous stirring. It is then cooled, with continuous stirring, to 40 C. At this point, the perfume is added and the mixture is then cooled, with continuous stirring to 25 30 C. to give the final product.

Example 7 A biocidally active tooth powder is prepared in the following manner:

Component: Parts by wt. Precipitated calcium carbonate 94.9 Powdered soap 5.0

Cetyl trimethyl ammonium cyclo hexy sulfamate 0.1

The above components are admixed at ambient temperatures to form a granular composition.

Example 8 An antiseptic lozenge is prepared as follows:

Component: Parts by wt.

Sucrose 73.0 Glucose solution in H 0 (50% conc.) 24.0 Glycerin 1.0

Alkyl dimethyl benzyl ammonium cycle hexyl sulfamate 2.0

The above ingredients are intermixed and the mixture 18 brought to a boil with constant stirring. It is then poured into molds and allowed to harden.

Example 9 A sun-tan cream with biocidal properties is prepared as follows:

The above components are intermixed at ambient temperature to form a homogenized cream.

Example 10 A biocidally active hair rinse is prepared in the follow mg manner:

Component: Parts by weight Glyceryl monostearate 3.0 Water 95.0 Cetyl trimethyl ammonium n-hexyl sulfamate 2.0

These ingredients are thoroughly intermixed at ambient temperature to form the final product.

Example 11 An antiseptic lozenge is prepared as follows:

Component: Parts by weight Sucrose 73.0 Glucose solution in H 0 (50% conc.) 24.0 Glycerin 1.0. Alkyl dimethyl ammonium cyclo hexyl sulfamate The above ingredients are mixed and the mixtureis brought to a boil while constantly being stirred. The mixture is then poured into molds and allowed to harden.

Example 12 A liquid shampoo with biocidal activity is prepared as follows:

The fatty acids are intermixed after which first the amine and then the propylene glycol is added. The mixture is then stirred until a clear solution is obtained, after which the alkenyl dirnethy ethyl ammonium n-hexyl sulfamate is added. All the mixing takes place at ambient temperature.

The above mixture is then diluted with Water to any desired consistency. During this addition of water, the mixture assumes a petrolatum-like consistency but gradually changes to a clear very slightly viscous solution. If the solution becomes cloudy, more of the amine is stirred in, a little at a time, until the solution again becomes clear. The final product preferably contains about 3 parts by weight of Water to 1 part by Weight of the above mixture.

Example 13 A biocidally active industrial cleaning composition is prepared as follows:

Component: Parts by Weight Newtral toilet soap, preferably Na or K soaps of stearic, palmitic or oleic acids (neutraP meaning no excess alkali) 30.0 Bentonite 30.0 Sodium lauryl sulfate 10.0 Lanolin 5.0 Perfume 1.0 Lauryl isoquinolinium n-hexyl sulfamate 1.5

A biocidally active wash solution is prepared as follows:

Component: Parts by weight Potassium tripolyphosphate 19.5 Sodium tripolyphosphate 5.0

Ultrawet L (alkyl aryl sulfonate anionic detergent produced by Atlantic Ref. Co.,

Phila., Pa). 33.0 Onyxol 336 (lauric acid alkanolamine condensate; a liquid detergent produced by Onyx Oil & Chem. 00., Jersey City, N. J.) 5.0 Canboxyl methyl cellulose 0.5 Alkyl dimethyl benzyl ammonium piperidine sulfam-ate-bromine complex containing 10% by Weight bromine 1.0

The above components were mixed together at ambient temperature to form the final product.

Unless otherwise specified, all parts and percentages described herein are by weight.

Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is, therefore, to be understood that within the scope of the appended claims, the invention may be practiced otherwise than as specifically described.

The invention claimed is:

I. Quaternary ammonium organic mono-sulfamate.

2. Quaternary ammonium n-hexyl sulfamate.

3. Quaternary ammonium aniline sulfamate.

4. Quaternary ammonium cyclo hexyl sulfamate.

5. Quaternary ammonium piperidine sulfamate.

6. A chemical complex consisting of a halogen and a quaternary ammonium organic sulfamate.

7. A bacteriocidal quaternary ammonium cyclohexylsulfam-ate.

References Cited by the Examiner UNITED STATES PATENTS 2,212,171 8/1940 Salzberg 260-567.6 2,383,617 8/1945 Robinson 260-501 2,732,393 1/1956 Hardy 260-501 2,746,986 5/1956 Sahyun et a1. 260501 2,809,146 10/1957 Osborn et al 16733 2,891,065 6/1959 Gundel 260293.4 2,926,119 2/1960 Niederhauser 16730 3,109,857 11/1963 Nomine et al. 260501 OTHER REFERENCES Butler et al.: Journal of the American Chemical Society, volume 61, pages 914915 (1939).

Hardy et al.: Journal of the American Chemical Society, volume 74, page 5214 (1952).

Suter et al.: Journal of the American Chemical Society, volume 65, page 5 12 (1943).

NICHOLAS S. RIZZO, Primary Examiner.

IRVING MARCUS, WALTER A. MODANCE, HENRY R. JILES, Examiners. 

1. QUATERNARY AMMONIUM ORGANIC MONO-SULFAMATE. 